Acid monoazo dyestuffs



A Franz Frisch,

United States Patent 2,998,418 CH) MONOAZO DYEST'UFFS Arlesheim, Baselland, Switzerland, assignor to Sandoz Ltd., Basel, Switzerland, a Swiss firm 1 Io Drawing. Filed Aug. 27, 1959, Ser. No. 836,334 Claims priority, application Switzerland Aug. 29, 1958 3 Claims. (Cl. 260-198) This invention relates to acid monoazo dyestufis of the general formula R stands for the hydroxy group, when R; is a phenyl radical, or, when R is hydrogen for an 3 -N zroup in which R is hydrogen or alkyl which may be sub stituted and R is either alkyl, aralkyl, cycloalkyl or aryl which may be substituted or, together with" N- and R a saturated heterocyclic radical, v

with the proviso that R, R and R .are sochosen that when R contains a large number-of carbon atoms the total number of carbon atoms in R and R shall be small, or

conversely that when R contains a'vs mall number of car'- bon atoms that total number of carbon atoms and} R shall be large.

The process ..for the production of the new acid mono-1 azo dyestufis consists in coupling 1 mole ofthe diazo g a 55 with stirring, and the resultlng solution is stirred into a compound of an amine of the general formula Or-kR wherein R possesses one of thc'aforecited meanings,

R-OS,

wherein R andR, each'possess one of the afore itedf meanings, in a strongly to weakly acid medium attemf peratures between 5 and 30 C.

Most of the new acid monoazo dyestuffs are obtained as red powders. They serve to dye and to print Wool, silk, leather and synthetic polyamide fibers and draw on these fibers from neutral to weakly acid baths in red to 5 'bordeaux shades which possess very good fastness to light and wet treatments (washing, water, sea water, perspiration, acid and alkaline milling). The dyeings also show good to very good fastness to acids, alkali, chlorine, peroxide bleaching, pressing crocking and dry cleaning and are well dischargeable. The dyestutfs also reserve well cotton, viscose filament yarn viscose staple fiber, cellulose-2 /2- and -triacetate and polyester fibers. The wet fastness properties are especially good whenthe molecular weight of the dyestulf used is higher than 600. To obtain dyestufis having good Wet fastness properties Z-amino- 8-hydroxynaphthalene-6-sulfonic acid methyl-amide for example, must be coupled with the diazo compound of a diazo component of Formula H containing a high molecular radical R, while the higher molecular coupling 20 components of Formula HI, in which e.g. R represents (2'.6'-dimethyl)-phenyl and R hydroxyl or R denotes hydrogen and R phenylamino in accordance with the above description, already in combination with the diazo compounds of diazo components of Formula II, in which R represents an unsubstituted phenyl of phenoxy radical or a low molecular monoor dialkyl amide radical, yield monoazo dyestuffs which have good to very good wet fastness properties.

Suitable coupling components of Formula III are the derivatives of Z-amino-8-hydroxynaphthalene-6-sulfonic acid in which the sulfonic acid group is closed by a substituted amide radical. The latter are obtained by the known methods from 2-acetylamino-S-hydroxynaphthalene-6-sulfonic acid chloride by reaction with primary or secondary amines and subsequent splitting-off of the acetyl group; examples are methylamide, dimethylamide, B-meth- ,oxyethyl amide, di-(,B-hydroxyethyD-amide, morpholide, and the phenylamide, N-methyl-N-phenylamide, N-ethyl- N-phenylamide or N-fl-hydroxyethyl-N-phenylamide of 2- 40 amino-8-hydroxynaphthalene-G-sulfonic acid. Other suitable azo compounds are 2-phenylamino-8-hydroxynaph- "thalene-G-sulfonic acids with a phenyl radical substituted in the 2-'.6' positions, preferably 2-(2'.6-dimethyl)-phenylamino 2- (2'.4'.6'-trimethyl) -phenylamino and 2- '-(2.4'.5'.6-tetramethyl)-phenylamino 8 hydroxynaphthalene-,6sulfonic acid.

In the following examples the parts and percentages "are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 50' ,41.1,parts of 3-amino-4-sulfobenzene-l-sulfonic acid- -'(4'-cyclohexyl)-phenyl ester are dissolved in 1000 parts of water with the aid of sodium hydroxide. A solution of 8 parts of sodium nitrite in 20 parts of water is added mixture of 200 parts of ice, 200 parts of water and 35 for 3 hours at 010, the precipitated diazo compound is v filtered on and washed with dilute hydrochloric acid.

with it 1 mole of a coupling component of general formula at ,.60..7.0 in a fine jet. The mass is stirred at 25-30 until coupling is completed, then the dyestufi is precipi- 'f -tated.with crystallized sodium acetate, filtered oil and "'dried'. It is a dark red powder which dissolves in hot ---water with a bright bordeaux-red coloration and dyes wool, silk and synthetic polyamide fibers from a neutral to weakly acid bath is in bright bordeaux shades of very good fastness to light and wet treatments.

EXAMPLE 2 36.4 parts of 3-amino-4-sulfobenzene-l-sulfonic aciddi-(n-butyD-amide are diazotized as described in Example 1. The diazo compound is filtered ofi, suspended in 800 parts of cold water and mixed with a solution at 60-70 of 37 parts of 2-(2.6'-diethyl)-phenyl-arnino-8- hydroxy-naphthalene-6-sulfonic acid in 200 parts of water, added in a fine jet. The mass is mixed at 25-30" EXAMPLE 4 '28 parts 'of 3-amino-4-su'lfobenzene-l-sulfonic acid dimethylamide are dissolved in 500 parts of water by means of sodium hydroxide. After the addition of a solution of 8 parts of sodium nitrite in 30 parts of water, 35 parts of concentrated hydrochloric acid are added at -5. After stirring for -3 hours at -10", the excess nitrous acid is destroyed with amidosulfonic acid and a solution of 32.8 parts of 2-amino-8-hydroxynaphthalene-6-suluntil coupling is completed and 30 parts of sodium acetate fonic acid N methyl N phenylamide in 100 parts of *f to Premiumte y It fi f tone is added dropwise. After a further 3 hours stirring, f 1f neqessary by re'dlssolvmg a @Preclpltatwn and a solution of 30 parts of crystallized sodium acetate in It a dark red Powder Whlch Elves blue-Ted $0111 100 parts of water is dropped in. Stirring is continued lions in hot Water and y W001, Silk and Synthetic P Y- for 6 hours, after which the acetone is evaporated and amide fibers from neutral to weakly acid baths in bright 15 the dyestufi precipitated and dried. It is a red powder blue-red shades with very good fastness properties to light which gives red solution in hot water and dyes wool, and wet treatments. silk and synthetic polyamide fibersin bright red shades which have very good fastness properties to light and wet E MPLE 3 treatments. 37.8 parts of 3-amino-4-sulfobenzene-l-sulfonic acid-n- The dyeing method is as follows: nonylamide are diazotized as described in Example 1 and 100 parts of wool fabric are entered in a dyebath at the filtered diazo compound is suspended in 500 parts of 40 composed of 5000 parts of water, 10 parts of anhywater at 0-5". A w soluti f 25,2 pal-ts f 2 drous sodium sulfate and 1 part of dyestuff. The bath 1S amino-8-hydroxynaphthalene-6-sulfonic acid methy heated to 100 in 15 minutes and maintained at this temamide in 500 parts of water and 15 parts of concentrated perature 20 Parts of a t hydrochloric acid is added dropwise. After stirring for g g q f t i. gfl 1S 2 hours at 10-20" a solution of 40 parts of crystallized ff g g g i g zi fi sodium acetate in 200 parts of water is dropped in slowly. I g y g p p constantly replaced. The dyed fabric is subsequently When the diazo compound has disappeared, the dyestuif 30 rinsed Wat and dried filtered 01f re-dissolved in dilute sodium carbonate solu- 1 er Further acid monoazo dyestuffs which are obtainable tion and reprecipitated, if necessary, and dr by procedures the same or similar to those of Examples It 1s a red powder which dissolves in hot water with a 1 to 4 are set out in t f ll i table, They r6d C fi d y W001, $11k f Synthetic P 3 spond to the General Formula I and are characterized by aml fibers 111 bnght red Shades havmg g t y the 'symbols'R,.R R and the shades of their dyeings on good fastness properties to light and wet treatments. wool.

Table Shade of Example No. R R, R the Wool 5 4'-iso-octylphen- H methylamino red.

0 6 yigrtamylphen- 2.6-dimethyl- 0H blue-red. 7 d gclohexy] Hphenyl. 2 h dro -eth 1- red amino. nun-"nu"? an iinof y I 8 n-'butylamino 'H n-hexylamino-- Do. 9...- (4-rnethoxy)'- H. dicyclo-hexyl- D0.

butylamlno. amino. 10 4-tert.buty1pl1en- -H ethylamlno Do.

0 11 dieg lamtno H di-(n-ibutyD- Do.

am I10- 12 n amylamino 2.4;6-trtmethy1- -0H blue-red. phenyl. hexylamino 2.4.5.6-tetrameth- -015 Do.

. t ylphenyl. heptylamino IH dlethylamtno red. n-octylamino H di-(2-hydroxy- Do.

ethyDamino. N-methyl-N- morpholino .Do.

phenylamino. N-2-hydroxy- .3'-methoxypro- Do.

ethyl-N-phenpylamino. ylamino. phenylamlno ethylamino... Do. cyclohexy1amino H. methylamino. Do. benzylamino H. .-..-do Do. 2-ethoxy-ethyl- N ethyl-N-phen- D0.

amino. ylamino. tsoamy1amino phenylamino Do. lsoamylamino cyclohexylamlnm- D0. dteth l min F heptylamino Do. (ii-(2 ydroxy- H n-octylamino Do.

ethyl-)amino. H morpholino H N-methyl-N- Do.

phenylamino. 3'-methoxypro- H N-2-hydroxyeth- Do.

pylamino. yl-I -pheny1- amino. lsobutylamino..... H henylamlno Do. diggiliggopyh- H enzylamino D0. N-ethyl-N-phen- H 2'-ethoxyethy1- D0.

ylamino. amino. phenylaminn "Ff methylamino...-. D0. dt-(3-hydr0xy H piperidino .Do.

propyl)-amlno.-

Table-Contmued Shade 0! Example No. R R, R the Wool Dyeing 83 3-methoxy-probenzylamino Red.

pylamino. 84 3-methy1phenyl- 4-methoxybuty1- Do.

amino. amino. 2-methy1-phen- H methylamlno Do.

oxy. 86 2'.4'-d1methyl- H (in Do.

phenoxy. 37 2'-meth oxyphen- H 1soamy1amino Do.

y mno. 3B di-(3-hydroxy- H n-buty1amino... Do.

propylamino). 9 4'-ehloropheny1- H methy1amino.-.--. Do.

amino. 40 2.5'-dich1oro- H do Do.

phenylamlno. 41 4'-chlorophenoxy H .-do D9. 42 2'.4'-d1ch10r0- H do Do.

phenoxy. 4a piperidinn H 3'-hydroxypro- Do.

pylamino. 44 benzylamlnn H 3'-methoxy-pro- D0.

pylamino. 45 3'-methoxy- 2'-methylpheny1- Do.

butylamino. amino. 46 dlethyl 4-methy1phenyl- Do.

amino. 47 M 2.4'-dimethyl- Do.

phenylamino. 48 fin 4-methoxy- D0.

phenylamino. cyclohexylamino d1-(3'-hydroxy- Do.

propyD-amlnO. n-buty1am1no....- 4-chlorophenyl- D0.

amino. 51 do FT 3'.4-dich1oro- Do.

phenylamino. 52 (in H 2-ch1orophenyl- D0.

amino. 3 (In H 2'.4'-dichloro- D0.

phenylamino. 54 phenylamino H n-propylamino..-- Do. an fin FT is Do. 56 d H is b yl D0. 57 phenyl H methylamino Do. 58 4-methylphenyl. H ethy1amino Do. 59 4'-ch1orophenyl. H 2-ethioxyethyl- Do,

am no. (in H methylamino D0. 61 phenyl Ff phenylamino D0. 62 do 2.6-gimefhyl- OH blue-m}.

P y 63 .-do 2.4.g-tl'inllethyl- OH D0.

. p eny M phenyl 2.4.5.6-tetrameth- OH----.-..-....- D0.

, ylphenyl. V 2-methy1phenyl 2.4.6-trimethyl- OH Do.

- phenyl. n-octylamino fin OH Do. ethylaminn H phenylamino red. 2'-hydroxy-- H 4'-chlorophen- D9.

ethylamino. ylamino. methylamino H 2.5-dich1oro- Do.

I phenylamino. n-propy1am1no.-.. H 2-ethylhexy1- 7 Do.

I amino. V isopropylamlno-.. H n-nony1am1no Do 4'-methy1pheny1- 2.6-dimethy1- OH blue-red. amino. phenyl.

2-eth ylhexyl- (in OH. D0.

ammo. 4'ethy1phenoxy-.. 2.4.g-triithyl- -0H D0.

p any 4'-lsopropy1- H di-(3-methoxyred. phenoxy. propylJ-amino.

Formulae of representative dyestuffs of the foregoing EXAMPLE 2 (OEa-GHy-Clh-CHOB S013 EXAMPLE O: HO l O:NHCH| (iso) EXAMPLE 6 (LO: HO

CnHn AOXH (tert.)

EXAMPLE 7 S 03H NH:

'8 Having thus disclosed the invention what I claim is: 1. An acid monoazo dyestufi of the general formula wherein R represents a member selected from the group 7 consisting of phenoxy, alkylphenoxy with 1 to 8 carbon atoms in the alkyl group and cyclohexylphenoxy, x represents a member selected from the group consisting of 7 hydrogen and methyl.

2. Themonoazo dyestuff of the formula 3. The monoazo dyestuff of the formula References Cited in the file of this patent UNITED STATES PATENTS 1,903,599 Schweitzer Apr. 11, 1933 2,205,849 Fischer et a1 June 25, 1940 2,638,403 -Stead et al. May 12, 1953 2,750,377 Hindermann et a1 June 12, 1956 2,776,962 Frisch Jan. 8, 1957 2,892,671 Alsberg et a1. June 30, 1959 OTHER REFERENCES .Colour Index, 2nd Ed. 1956, Society of Dyers and Colourists, vol. 1, page 1001, under The Nun-Textile Usage; POSL. 

1. AN ACID MONOAZO DYESTUFF OF THE GENERAL FORMULA 